Multiphase acrylic modifiers for vinyl halide polymers

ABSTRACT

Vinyl halide polymers characterized by superior mill roll release at high temperature and resistance to &#39;&#39;&#39;&#39;plate out,&#39;&#39;&#39;&#39; are attained by modifying the polymers with a multiphase acrylic composite polymer comprising (A) a first non-crosslinked phase of molecular weight of up to 450,000 polymerized from a first monomer emulsion or solution of at least 25 weight percent of at least one alkyl acrylate, wherein said alkyl group has 1 to 18 carbon atoms, 0 to 75 weight percent of another acrylic monomer and 0 to 75 percent of another copolymerizable ethylenically unsaturated monomer, and (B) a final, rigid thermoplastic phase polymerized in the presence of the first phase from an emulsion or solution of about 35 to 100 weight percent of at least one monomer which is a methacrylate, acrylate, styrene or substituted styrene, 0 to 65 weight percent of another acrylic monomer, and 0 to 65 weight percent of another copolymerizable ethylenically unsaturated monomer, wherein the rigid thermoplastic phase has a molecular weight of from about 400,000 to about 5 X 10.hu 6.

United States Patent 1191 Carty et al.

1111 3,859,384 14 1 Jan. 7, 1975 MULTIPHASE ACRYLIC MODIFIERS FOR 'VINYL HALIDE POLYMERS [75] Inventors: Daniel T. Carty, Willingboro, N.J.;

James A. Oline, Wyncote, Pa.

[73] Assignee: Rohm and Haas Company,

Philadelphia, Pa.

[22] Filed: Oct. 20, 1972 [21] Appl. No.: 299,492

Related US. Application Data [63 Continuation of Ser. No. 108,177, Jan. 20, 1971, abandoned, which is a continuation-in-part of Ser. No. 55,979, July 17, 1970, abandoned.

[52] US. Cl 260/876 R, 260/23 ST, 260/23 AR, 260/23 XA, 260/31.6, 260/3l.8 M, 260/881, 260/884, 260/885, 260/886, 260/899, 260/901 [51] Int. Cl. C08f 15/00, C08f l9/00 [58] Field of Search 260/876, 885

[56] References Cited UNITED STATES PATENTS 3,04l,308 6/1962 Baer 260/876 R 3,251,904 5/-l966 Souder et al 260/876 R 3,041,809 6/l962 Baer 260/876 R l/l970 Baer et all 260/879 Primary Examiner-John C. Bleutge Assistant Examiner-Richard B. Turer Attorney, Agent, or Firm-Michael B. Flin [5 7] ABSTRACT Vinyl halide polymers characterized by superior mill roll release at high temperature and resistance to plate out, are attained by modifying the polymers with a multiphase acrylic composite polymer comprising (A) a first non-crosslinked phase of molecular weight of up to 450,000 polymerized from a first monomer emulsion or solution of at least 25 weight percent of at least one alkyl acrylate, wherein, said alkyl group has l'to 18 carbon atoms, 0 to 75 weight 3 Claims, N0 Drawings MULTIPIIASE ACRYLIC MODIFIERS FOR VINYL HALIDE POLYMERS This is a continuation of application Ser. No. 108,177

filed Jan. 20, 1971, and now abandoned, which, in turn,

a continuation-in-part of Ser. No. 55,979, filed July 17, 1970, and now abandoned.

Vinyl halide polymers are a class of materials well known in the art, and are widely used for their excellent balance of physical properties, economy, and availability. Included are homopolymers and copolymers of vinyl halides generally, and particularly the polymers and copolymers of vinyl chloride. The copolymers contemplated in the art by the expression vinyl halide copolymers typically comprise the polymers resulting from the polymerization of a monomer mixture comprising at least 80 percent by weight 'of a polyvinyl halide with up to about percent by weight of another monovinylidene compound copolymerizable therewith, such as vinyl acetate, methyl methacrylate, styrene or the like. I

The usefulness of vinyl halide polymers can be increased by physically blending various modifiers with the polymers prior to use for plastic objects. These additives include materials such as lubricants, stabilizers, toners, fillers, pigments, crosslinking agents, tackifiers, plasticizers, processing aids, impact modifiers, and"de- I flection temperature under load improvers. The presentinvention however is concerned only with the performance of rigid and plasticizedvinyl halide polymers containing resinous modifierswhich function as processing aids; The modifierswhen added to'vinyl halide polymers producea substantial improvement in the processing behavior of the polymers particularly in calendering, milling and rolling.

Conventionally, styrene/acrylonitrile copolymers, or styrene/alkyl methacrylate interpolymers have been used to improve the processing characteristics of vinyl halide polymers during operations such as milling, calendering or the like as exemplified by Jennings, U.S. Pat. No. 3,646,417 and Schwaegerle, U.S. Pat. No. 2,791,600. In order to increase production and, in some cases, to produce a product of particular desirable properties which are promoted by rapid operation, it is often desirable to conduct milling, calendering or like operations at higher than conventional rates. Such higher rates of operation, however are accomplished by higher temperatures temperatures at which the conventional aids begin to lose their process-lubricating qualities. As a result, the vinyl halide polymer develops a tendency to adhere to equipment surfaces. It has been found that the modifiers of the present invention, which are alkyl acrylate-hard phase composite poly mers of particular compositions and properties, when added to vinyl halide polymers, impart superior. mill.

roll release at high temperatures and resistance to plate out." I

Souder et al., U.S. Pat. No. 3,251,904, shows a polyvinyl chloride (PVC) modifier of (I) 60 to parts of methyl methacrylate or methyl methacrylate and another monomer and (II) 40 to. 75 parts alkyl acrylate polymers or polymers of an alkyl acrylate and another monomer. Netherlands 69/05725 (Monsanto) shows a modifier of PVC that is an alkyl acrylate homopolymer and/or a copolymer of 5 to 95 weight percent alkyl acrylate and 95 to 65 weight percent of another alkyl acrylate as a processing aid. United States pending application, Ser. No. 31,754 filed 4/24/70, Ryan, describes a PVC modifier which comprises a first cross-linked acrylic elastomer phase and a second acrylic rigid phase. The modifier imparts low die swell characteristics to the PVC. United States pending application, Ser. No. 42,882, Whang, shows polymeric modifiers of molecular weights of from 1,500 to less than 10,000 containing the residue of (A) from to percent by weight alkyl methacrylate and (B) from 0 to 25 percent of at least one ester of acrylic or methacrylic acid, styrene or substituted styrene.

The prior art does not teach the particular composition of the modifiers of the present invention and the superior mill roll release and resistance to plate out imparted by the modifiers to vinyl halide polymers.

Plate out or roll plating or die-lip deposit has plagued processors from the earliers days of vinyl halide polymer compounding. The build-up of a deposit of incompatible materials on metalprocessing or finishing surfaces ismore than an annoyance. Changes inproduct, appearance, contamination, and disruption of production due to plate out cost money.

Another problem encountered inmilling, calendering, extrusion and like operations as applied to vinyl halide polymers is the tendency of the polymer to adhere to processing surfaces at high temperatures. In many operations, it is advantageous to operate at high processing temperatures to increase throughput and to produce a product of certain desired properties. However, at these processing'temperatures, vinyl halide and about 2 to 50 weight percentof a multiphase acrylic composite polymer comprising (A) a first noncrosslinked soft" phase of molecular weight of up to 450,000, preferably 7,500 to 50,000 polymerized from a first monomer emulsion or solution of at least 25 weight percent of at least one alkylacrylate wherein the alkyl group has 1 to 18 carbon ,atoms, 0 to 75 weight percent of another acrylic monomer, and 0 to .75 percent of another copolymerizable ethylenically unsaturated monomer, and (B) a final, rigid thermoplastic phase polymerized in the presence of the elastomer phase from a second monomer emulsion or solution of about 35 to 100 weight percent of at least one monomer which is a methacrylate, acrylate, styrene or substituted styrene, 0 to 65 weight percent'of another acrylic monomer, and 0 to 65 weight percent of another copolymerizable ethylenically unsaturated monomer, wherein the rigid thermoplastic phase has a molecular weight of from 400,000 toabout 5 X 10 The composite polymer material is ordinarily and preferably prepared by emulsion or solution polymerization of the first phase as a discrete phase from a monomer composition of 'at least 25 weight percent of an alkyl acrylate with an alkyl group of l to 18 carbon atoms. Upon completion of the polymerization of the first phase, i.e., substantial exhaustion of the monomers in the initial polymerization composition, the rigid thermoplastic phase is then formed by polymerization in the presence of the first phase, in the same emulsion or solution, from a 'monomer mix comprising at least near the surface of the first phase as hereinafter more fully described, and'without the formation of substantial numbers of new particles in the emulsion.

The first stage of the polymers of the present invention may be polymerized from a mixture containing 25 to 95, or preferably 35 to 45 weight percent ofat least one alkyl acrylate wherein the alkyl group has 1 to 12 carbon atoms; Preferred alkyl acrylates include butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.

The first or soft phase may be polymerized from a monomer emulsion or solution containing to 75 weight percent of another-acrylic monomer or between 35 to 65 weight percent monomer which may be acrylonitrile, methacrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N- methylol acrylamide, octyl acrylate, chloroethyl acrylate, alkylthioalkyl acrylates such as ethylthioethyl acrylate, and the like, alkoxyalkyls such as methoxyethyl acrylate, and the like, and alkyl methacrylates wherein copolymerizable ethylenically unsaturated monomer.

Such copolymerizable monomers include styrenes such asstyrene, p-chlorostyrene, nitrostyrene, and a-methyl styrene;.vinyltoluene; alkyl vinyl ethers; alkyl vinyl ketones'; chloroethyl vinyl ethers, and the like. In one particular embodiment of the present invention, the vinyl halide polymers characterizedby superior mill roll release and resistance, to plate out are modified with non-crosslinked polymers of molecular weight of up to 450,000 polymerized from a monomer mixture of the alkyl acrylate described above and a member selected from the group consisting of acrylonitrile, methacrylonitrile, styrene, and substituted'styrenes. In this embodiment no final, rigid'thermoplastic' stage is used.

Most prefer'redsoft stages within the scope of the present invention include acrylic interpolymers prepared from monomer mixtures comprising about to 100 parts by weight butyl acrylate and ethyl acrylate monomers, about 0 to 64 parts by weight other acrylic monomers, and about 0 to 65 parts by weight of other non-acrylic ethylenically unsaturated monomers. An example of a most preferred soft stage is a polymer of about less than 40 percent by weight butyl acrylate,

about less than percent styrene, about 3 percent methylmethacrylate and less than 1 percent ethyl acrylate.

The soft stage of the present invention must have a molecular weight of up to 450,000. Compositions of molecular weights outside of this range do not impart the resistance-to plate out and most importantly do not.

impart the superior mill roll release characteristics to vinyl halide compositions which are critical features of ular wei g ht refers to viscosity average molecular weight (M,,). The elastomeric phase of the multiphase acrylic composite interpolymers of this invention may be defined in terms of its characteristic. It should be noted that although the characteristic molecular weight range for the present elastomers is a critical feature of the present invention, novelty resides, not here alone,

but rather in the manner in which this feature interdependently and cooperatively combines with the final rigid thermoplastic phase to produce a modifier which imparts to vinyl halide polymers the surprising characteristics of superior mill roll release, and resistance to plate out. It has also been found that the multiphase acrylic composite interpolymers, in addition to imparting mill roll release and resistance to plate-out, additionally may provide a polyvinyl chloride system of excellent clarity.- Furthermore, the present modifiers are easily isolated through spray drying and are quite suitable for powder blending.

The rigid thermoplastic phase of the composite interpolymer of the present invention includes the .acrylic thermoplastic polymerized from monomer. mixtures comprising 35 to 100 weight percent of at least one monomer which is a methacrylate, acrylate, styrene or substituted styrene, one or more acrylic comonomers in quantities of 0 to weight percent, and 0 to 65 weight percent of another ethylenically unsaturated monomer. The thermoplastic phase may be polymerized from a monomer mixture containingSO to weight of at least one monomer which is the methacrylate, acrylate, styrene or substituted styrene. Suitable methacrylates and acrylates include alkyl and aryl esters of methacrylic and. acrylic acid wherein the alkyl group may be straight chain, branched chain, or cycloalkyl. The cycloalkyl' group may be either bridged or unbridged. The term aryl includes aralkyl and alkaryl groups which may be substituted,if desired, on both the aliphatic portions and on 'the aromatic portions. The alkyl acrylates and methacrylates usually include those wherein the alkyl group contains 1 to 18 carbon atoms and the cycloalkyl acrylates are usually those wherein the cycloalkyl group contains 4 to 10 carbon .atoms. In the preferred alkyl acrylates and methacrylates, the alkyl groups contain 1 to 4 carbon atoms. Examples of alkyland arylmethacrylates and acrylates include methyl methacrylate, ethyl methacrylate, npropyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, stearylmethacrylate, phenyl methacrylate, ben zyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, nobornyl methacrylate, fenchyl methacrylate, isofenchyl methacrylate, bornyl methacrylate, the corresponding acrylates and the like. Suitable substitutions on these methacrylates include halogen (e.g. chlorine), hydroxy, alkoxy (e.g. methoxy), alkylthio (e.g. ethylthio), cyano,

and the like.

When substituted styrene is utilized as a component, the substituents usually are from about 1 to 5,"preferably about 1 to 3 carbon atoms in chain length, but may be other non-deleterious substituents. Exemplary of the substituted styrenes useful in the acrylate polymers of the present invention are a-methyl styrene, chlorostyrene, a-hydroxy methyl styrene, and the like. Exemplary substituents for such compounds are halogens, hydroxy groups, alkoxy groups, as well as lower alkyl groups, etc.

The rigid thermoplastic phase is polymerized from monomer mixtures containing to 65 weight percent or to weight percent of other acrylic comonomers such as other alkyl and aryl methacrylates alkyl and aryl acrylamides, substituted alkyl and aryl acrylic and methacrylic monomers, where the substituents can be halogen, alkoxy, alkylthio, cyanoalkyl, amino alkylthio, and other like substituents. The final rigid phase is prepared from monomer mixtures which also contain 0 to 65 or 5m 15 weight percent of another ethylenically unsaturated monomer which imparts a rigid character to the rigid phase, such as vinyl aromatics, preferably styrene and a-methylstyrene, vinyl and vinylidene halides, and vinyLsubstituted nitriles, vinyl esters, vinyl ethers, vinyl amides, vinyl ketones, olefins, and the like.

'An example ofmultiphase acrylic composite polymer for the purpose of this invention is the product of the polymerization of a mixture of about 60 weight percent soft stage polymer, about 35 percent methyl methacrylate, about 4 percent ethyl acrylate, less than about 1 percent butyl acrylate and less than about 1 percent styrene.

The rigid phase is further-characterized by molecular. weight ranging from about 400,000 to 5 X 10, preferably 750,000 to 3 X 10 A particularly effective molecular weight for attaining the full benefits of the present invention isabout 750,000 to l X 10, which level is also relatively convenient .to attain in preparing the composite interpolymers of the present invention.

The modified compositions of the present invention may contain from 75to 99.9 percent by weight of a vinyl halide polymer modified with from about 0.1 to percent by weightof the multiphase acrylic composite interpolymer modifier, Usually, however, and particularly when the modified compositions are used in a milling or calendering operation, the amount of modifier varies from 1 to about 10 percent by weight, preferably about 2 to 4 percent by weight. The modifiers of this invention comprise from 50 to 90 percent by weight of the lower alkyl acrylate-containing phase, from 10 to 50 percent by weight of the final rigid thermoplastic phase. In its preferred composition, the modifiers of the present invention contain from 50 to 70 percent by weight of the first phase and from to 50 percent by weight of the thermoplastic phase. The above percentages are based on the total multiphase acrylic composite interpolymer modifier content of the vinyl halide polymer material.

The composite acrylic interpolymers of the present invention are prepared by solution, suspension or emulsion polymerization procedures utilizing a multi-stage or sequential technique. In simplest form thefirst phase is formed in an initial stage and the rigid thermoplastic phase is formed in a second stage. Either the first or rigid phases can themselves also be sequentially-polymerized. The monomers of the initial stage, together with polymerization initiators, soap or-emulsifiers polymerization modifiers and chain transfer agents and the like are formed into the initial polymerization mix and polymerized, e.g. by heating and mixing the emulsion, in well known and wholly conventional fashion, until the monomers are substantially depleted and a seed polymer is formed. Monomers of the second, and in turn, of each additional stage are then added with appropriate other materials e.g. supplementary initiators, soap, modifiers,,and the like, so that the desired polymerization of each stage occurs in sequence to substanthe C and C and higher alkyl mercaptans particularly tial exhaustion of the monomers. in each stage subsequent to the first, the amounts of the initiator and soap, if any, are maintained at a level such that polymerization occurs at or near the surface of the existing particles, and no substantial number of new particles, or seeds, form in the emulsion. When the phases of the composite interpolymer are either themselves formed by sequential polymerization, the monomer constituents of the various stages of each phase may vary from stage to stage, or all'the components can be present throughout the entire phase polymerization. The stages can vary in hardness, from a very soft elastomer first stage seed to the hardest rigid thermoplastic. Both the elastomer and the rigid thermoplastic can contain chain transfer agents, in one or all stages, and, if desired the rigid thermoplastic stage can contain polyfunctional crosslinking monomers. However, it is a characteristic of the present invention that the first soft is non-crosslinked. What is meant by the term non-crosslinked" is that no cross linking monomers are present in the elastomer stage.

As already described, and as will be shown in the examples infra control of the molecular weight of the first phase up to 450,000 is essential to the present invention. Preferably the molecular weight is in the range of 7,500 up to 50,000 or to 450,000. It has been found that excellent polyvinyl halide processing modifiers. result from compositions where the molecular weight of the first stage is of this critical range. Numerous techniques are known for control of molecular weight and there is not criticality in the present invention in any particular technique however a preferred techniqueis the use of a chain transfer agent such as an alkyl mercaptan in the polymerization mix of the first stage or stages in which the elastomeric phase is polymerized.

Suitable chain transfer agents in this invention include n-dodecyl mercaptan. Other techniques for controlling molecular weight of the elastomeric phase include the use of peroxide, operations at high temperatures or the use of allyl compounds.

The polymerization, reactions can be initiated by eibenzene hydroperoxide, and the like, with a reducing agent, such as a sodium, potassium, or ammonium bisulfite, metabisulfite, or hydrosulfite, sulfur dioxide, hydrazine, ferrous salts, ascorbic acid, sodium formaldehyde sulfoxylate and the like, as are well known in the art.

Examples of emulsifiers or soaps suited to polymerization processes of the present invention include alkali metal and ammonium salts of alkyl, aryl, alkaryl, and

aralkyl sulfonates, sulfates and polyether sulfates, eth-' oxylated fatty acids, esters, alcohols, amines, amides, alkyl phenols, complex organophosphoric acids and their alkali metal and ammonium salts.

The thermoplastic vinyl halide polymers utilized in the present invention are the polymers and copolymers of vinyl halides, preferably chlorides, widely utilized in the production of plastic articles. These polymers are referred to as vinyl halide or vinyl chloride polymers in the present invention, and for most all uses must be modified, compounded or copolymerized with other materials to provide processable and useful compositions. For the purposes and scope of this specification the term vinyl chloride polymers or compositions will include all compositions which have vinyl chloride or other halide as the major (greater than 50 percent) component monomer. The compositions include but are not limited to: poly(vinyl chloride) [PVC], copoly-' mers of vinyl chloride with other monomers that include vinyl alkanoates such as vinyl acetate and the like, vinylidene halides such as vinylidene chloride, alkyl esters'of carboxylic acids such as acrylic acid, ethyl acrylate, 2-ethylhexyl acrylate and the like, unsaturated hydrocarbons such as ethylene, propylene, isobutylene and the like, allyl compounds such as allyl a'cetate and the like; for flexibility vinyl halide polymers are often compounded with plasticizers such as dioctyl phthalate, poly(propylene adipate) and the like, and

other modifiers such as chlorinated polyethylene; and

manyother materials are often included. The molecular weight andv molecular weight distribution of the polymers is not critical to the aims, purposes and results of using this invention. For general applications vinyl chloride polymers with Fikentscher K-values in the range of 40 to 95, preferably about 50 to 75, are generally used. The Fikentscher K-value is determined in the formula polymer processability to polyvinyl halides at high temperatures but theselubricants adversely affect clarity of the polytate. The most preferable copolymer contains up to 10 weight percent of the comonomer, with the remainder being vinyl chloride.

The copolymers of vinyl chloride and another monomer, mentioned above, are often softer than homopolymers of vinyl chloride.

Finally, the most preferred polymer, and the polymer which is most effectively modified by the composite interpolymers of thepresent invention is the homopolymer of vinyl chloride.

The above copolymersvary in physical characteristics such-as viscosity, and molecular weight. The copolymers generally are of slightly lower molecular weights than PVC. Also, the viscosity values are often slightly lower, although generally within the above range. These differences however, are not limiting to the present invention which is directed to modifying such polymers and not the polymers themselves. The polymers, however, as is obvious, must be suitable for the use desired when modified, and physically mustbe Blends of the composite interpolymer and the vinyl halide polymer can'be accomplished by any convenient technique. Entirely satisfactory blends can be accomplished on a roll mill'at convenient and customary operating conditions, such as about 350F. in about 5 minutes or less time. Dry mixing techniques, as with a mechanical mixer-blender device, can alsobe employed. The powder blends can, if desired, be processed in'com'merical extrusion equipment at-conditions varying with the molecular weight of the polyvinyl halide used and the equipment employed for that purpose. s

Certain processing aids, stabilizers, and the like are often incorporated in the blends, The stabilizers which serve to prevent the breakdown of the polyvinyl halide,

without any of these other conventionaljlubricants. In

some instances however, it 'may be advantageous to utili ze the compositions 'of the present invention with lubricants. In such cases suitable lubricants include stearic acid, stearyl alcohol, licosanol, and other known types. Certain known lubricants may impart improved mers. This point will be illustrated in the examples of this specification by a comparison between compositions containing a conventional lubricant and compositions containing the acrylic composite interpolymer of this invention.

Other inclusions of the blends prepared in accordance with the present invention include colorants, including organic dyes, such as anthraquinone red, and the like, organic pigments and lakes such as phthalocyanine blue and the like, and inorganic pigments such as titanium dioxide, cadmium sulfide, and the like; fillers and particulate extenders such as carbon black, amorphous silica, asbestos, glassfibers, magnesium carbonate, and the like; plasticizers such as dioctyl phthalate,

dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, and the like; and impact modifiers such as typical methacrylate/butadiene/styrene modifiers and others.

While only a few of suchmaterials have been specifically recited, it is not intended to exclude others, the recitation is exemplary only, and each category of additives is common andwell-known in the art, including tion in accordance with accepted techniques wellknown to those ordinarily skilledin the art, in p'ropor-' tions which are commonly employed. Such additional of a type to which the present modifiers can be added.

materials are not of particular significance in the present invention and form no part thereof.

To assist those skilled in the art in the practice of the present invention, the following modes of operation are set forth as illustrations, parts and percentages mean by weight unless otherwisespecifically noted:

EXAMPLE I The following procedure illustrates a process for making the multiphase acrylic composite polymers of the present invention. The polymer illustrated is char- 5 acterized by a butyl acrylate/styrene (40/60) first stage and a methyl methacrylate/ethyl acrylate (45/5) second stage value where this ratio of the first stage to the second stage is 1/1.

of the emulsion was spray dried with good recovery and good product to dusting ratio.

EXAMPLE II The composition prepared in Example I and other polymers indicated in Table I and prepared according to the same general procedure are incorporated into polyvinyl halide compositions by the following procefiltered through cheesecloth. An aliquot of the emulsion is evaporated in a vacuum oven for 2 to 3 days at 60 C. to yield a solid of [1;]acetone The balance Two parts of acetic acid (5 percent aqueous solution) dure: and 881 parts of distilled water are mixed under nitroone hundred grams of a hand P l of gen with stirring. The temperature is adjusted to 40C. polyvmyl chlonde 3 parts of modlfier mdl-cated and 82 parts of a monomer mixture is added The 1n the Table I, 2 parts of atln stablllzer, and 1.0 parts monomer mixture contains 5 parts acetic acid (5 perlubrgcamst W at 26/20 for 3 mmutes at cent aqueous solution), 3.5 parts of a 20 percent aque- 50 h i fg f gg 9T E 86; by mlllous solution of sodium lauryl sulfate, 1.5 parts of an 80 minutes t h z percent concentrate of the primary phosphates of ocgggg gi z m o me t s i tylphenoxypolyethoxyethanol in water, 170 parts of two 2? 8 a F f f: y? distilled water 15 parts mdodecyl mercaptan 200 utes coo l irf under r zs l l ie D urih ti hi h t3: i:- parts n-butyl acrylate, 300 parts styrene and 5 parts cug g g p6 meme h dro eroxide A Solution (26 arts) f 1 t ture mllllng operation, the samples are rated for roll rey p p 0 lease according to thefollowing system: sodium sulfoxylate formaldehyde in parts water 1s added and the nitrogen sparge is reduced. Over 1.5 p (pom) ,only edgesofswck can be hours an addltlonal 618 parts of the above monomer 25 F (f removed W difficully mix are added. After the reaction is completed, the 2315222213 the Stock product is filtered and the emulsion is evaporated in a 6 (g most 0; the stock can be retlt tlfl l vacuum oven for 2 to 3 days at 60 C. to give a seml- E (excellent) g gT fg solld materlal, [17]acetone with no sticking Distilled water, 484 parts and 796 parts of an emul- 30 sion of the preceding-prepared polymer (250 parts These samples are also rated for mill stability and clarsolids) are mixed under nitrogen sparge. The temperaity of final sheet according to standard tests.

Table I Mill Intrinsic Roll Stability Clarity Viscosity Release Min. Color Per- Perin At 1 M3 to at cent cent Composition Acetone Min Min Color 3 Min. WL Haze Unmodified Polyvinyl Chloride F P' 1% yellow 80.0 11.2 A 0.78 E+ E+ 1 yellow 79.5 14.2 B 0.11 E+ E+ 1% yellow 80.2 13.2 C F+ P+ 1% yellow 70.0 15.0 D 0.83 E+ 12+ 1% yellow 79.0 12.3 D 0.87 15+ E+ 1% ellow 80.5 11.8 D 1.0 E+ E+ 1% ellow. 81.2 15.1 D 0.84 E+ E+ 1% yellow 70.0 18.9 D 0.91 15+ E 1% yellow 78.4 9.9 D 1.0 E G- 1% yellow 78.0 15.1 D 1.3 0+ G 1% yellow 70.8 12.9 D 1.3 oo- 1% yellow 82.2 8.2 D 1.3 G- o- 1% yellow 82.2 8.2

ture is ad'usted to 44-45C. and a solution (26 arts) Com osition A contains the modifier pre ared in Ex- J g P P P of 1 part sodium sulfoxylate formaldehyde 1n 25 parts ample I, B contains a low molecular weight water is added. ,A monomer mixture, 359.63 parts, is vp0 y tyl acrylate/N-vinyl pyrro d n then added to the reaction mixture over a period of 95/5, C contams a styrene/butyl acrylate; about one hour. The mixture contains 1.25 parts of an p y modifier and D Contains a Styrene/but}ll percent concentrate of the primary phosphate of oclate first flm y methacrylate Second Stage; tylphenoxypolyethoxyethanol in water, 108 parts of 60 30/20/50- distilled water, 225 parts methyl methacrylate, 25 parts ethyl acrylate and 0.38 parts cumene hydroperoxide. EXAMPLE The resulting P y y l y e/m y Various modified polyvinyl chloride compositions methacrylate/ethyl acrylate; 2 5/ 1S Cooled d 65 are prepared by milling grams of mixtures of modifier and polyvinyl chloride for five minutes at 425F., 21/20 rpm. roll sheets followed by compression molding into one-eighth inch thick slabs at 350F. according to a cycle of a three-minute preheat; two minutes com- I pression at 70 ton pressure followed by three minutes cooling under pressure. Table II shows processing resuits and clarity determinations for the various modified compositionsjndicated.

. Composition A contains a 30 parts styrene/ parts butyl acrylate first stage and a 50 parts methyl methacrylate second stage polymeric modifier, composition B contains a low molecular weight (M 14,000) polybutyl acrylate, C contains a styrene/butyl acrylate; 60/40 copolymer modifier and D contains 'a parts styrene/20 parts butyl acrylate first stage and a parts methyl methacrylate/S parts ethyl acrylate second stage polymeric modifier. Compositions A and D are prepared in accordance with the procedure of Example weight, a small percentage of n-dodecylmercaptan is added to the first stage monomer mixture.

This example illustrates the effect of varying molecular weight on processing and compositionalproperties.

EXAMPLE IV In this example, the polymers shown in Table III are prepared in accordance with the procedure of Example l. The polymers are then incorporated into polyvinyl chloride compositions by'the procedure of Example 11 and are tested for roll release and mill stability at 425F. and 380F. with the results as shown in Tables Iexcept that where necessary to control molecular 1V and TABLE I1 Intrinsic Processing Percent Viscosity Flex Rolling Hot White Light Percent Composition ln Acetone Time Bank Strength Thermoplasticity Release Transmission Haze (Minutes) I Unmodified Polyvinyl Chloride 2 F F F G 86.4 5.7 A 0.83 2 G+ G+ G E 84.0 6.0 A 0.87 2 G+ 6+ 6+ E 87.0 6.9 A 1.0 2 (1+ G+ G E 87.5 4.9 A 0.84 2 'G+ G+ G+ E. 86.0 7.6 A 0.91 1% 0+ G+ G+ E- 89.0 5.1 A 1.0 1% G+ G+ G E- 87.5 6.5 A 1.3 1% G+ G+ G E- 83.0 10.6,- A 1.3 1% 0+ 6+ 0+ E- .846 9.0 v A 1.7 1% 6+ G+ G+ E- 86.2 5.8 B 1% G G F+ E+ 84.5 5.9 C 0.11 3 F+ F+ F+ E+ 85.0 9.4 D 0.96 2 0+ G G E+ 87.0 5.7

Table III Composition Intrinsic Intrinsic Ratio of Viscosity Viscosity First Final First Stage/ In Acetone In Acetone Stage Stage Final Stage First Stage for Polymer A styrene/ methyl butyl methacrylate/ acrylate; ethyl acrylate;

,30/20 45/5 /50 0.11 0.96 B styrene! methyl butyl methacrylate/ acrylate; ethyl acrylate 7 36/24 36/4 /40 0.13 0.91 C styrene/ methyl butyl methacrylate/ acrylate; ethyl acrylate Stage I Q Stage 11 Sample [1;]acetone .M,, X 10 [wflacetone M, X 10 A 0.11 1.8 0.96 1.62 B 0.13 1.9 0.91 1.91 C 0.12 1.85 0.53 1.02

Table IV Mill Stability Percent of Roll Release Minutes Color- Total Polyvinyl At 1 At 3 to i at 3 Composition Chloride Composition Minute Minutes Color Minutes Unmodified Polyvinyl Chloride P P- 1 orange A I 'E- G 1% yellow A 2 0+ G 1 /4 yellow A 3 E- E 1% yellow Table IV Continued Mill Stabilit Percent of Roll Release Minutes Color Total Polyvinyl At 1 At 3 to at 3 Composition Chloride Composition Minute Minutes Color Minutes B 1 E 1% yellow B 2 E E1- 1% yellow B 3 E E+ 1% yellow C l E- E 1% yellow C 2 E- 15+ 1% yellow C 3 E El- 1% yellow Table V Processing Percent Static Heat Percent of White Stability 380" C. Polyvinyl Flex Light Minutes Minutes Chloride Time Rolling Hot Thermo- Trans- Percent to to Composition Composition (Minutes) Bank Strength plasticity Release mission Haze Color Char Unmodified I Polyvinyl Chloride V4 V; F F F G 75.8 16.2 10 80 A 1 54 A F+ F+ F+ G 81.1 10.6 20 90 A 3 A A F+ G- G- G 79.0 12.7 20-30 90 A 5 V4 A F+ G G G 81.1 13.1 20-30 90 B l y /4 k F+ F+ F+ G 79.6 12.6 -20 90 B 3 A A F+ G- G- G 80.5 13.1 -30 90 B 5 A k F+ G G G 84.1 7.3 20-30 90 C 1 V4 k F+ F+ F+ G 83.5 8.4 10-20 90 C 3 V4 V; F F+ F+ G 81.6 9.6 20-30 90 C 5 V4 k F+ F+ F G 80.6 10.0 20-30 90 EXAMPLE V determined after 7 minutes milling-at 350F., 26/20 In this examples a multiphase acrylic composite polymer of the composition; first stage, 50 parts butyl acrylate; final stage, 45 parts methyl methacrylate/S parts ethyl acrylate, is prepared in accordance with the procedure of Example I. The polymeris then incorporated into a polyvinyl chloride composition by the procedure Table VII of Example II and is tested for roll'release and mill sta- C s mzi g 32 Y ra bility at 425F. with the results as shown in Table VI. mp0s e ease lg Table VI Roll Release Heat Stability Clarity Percent At Relative Percent Modifier in 1% 2 At 5 Minutes Stability at White Light Percent Composition Polyvinyl Chloride Minutes Minutes to Color 5 Minutes Transmission Haze Unmodified Polyvinyl Chloride P 4 P P 80.0 8.8

butyl acrylatel/ methyl methacrylate/ ethyl acrylate (/145/51 5 6+ 0+ 1% 2 G- 29.6 93.2 3 0+ G 1% 2 G- 45.5 58.7 1 G 0+ 1% 2 6+ EXAMPLE VI Unmodified 6O Polyvinyl P- 87.5 6.9 As pointed out above 11'] the specification the process- A B 87.0 4.0, ability of polyvinyl halide compositions can be im- 3 5; 1; proved with conventional lubricants at the expense of V L clarity. The following example illustrates the foregoing, comparing a conventional lubricant with a composition styrene/butyl acrylate (n-dodecyl mercaptan) second of the present invention. Table Vll shows polyvinyl halide compositions containing the respective lubricants or modifier. In each instance, roll release is determined after 3 iits m lliasa 4. .595 2 12. rP Clarity is stage: methyl methacrylate/ethylacrylate;36/24 (3percent)//36/4. The composition contains 97 parts polyvinyl halide, 3, parts of the modifier; 2.0 parts of a tin stabilizer 0.8 parts of a-glycerol monostearate internal lubricant and 0.2 parts of a fatty acid ester lubricant. Composition B contains 100 parts polyvinyl chloride, 2 parts of the tin stabilizer, 1 part of a low molecular 16 t ity at 425F. with results substantially the same'asthose' obtained with the composition of Example I, shown in Table I.

Table VIII Mill Stability Roll Release Minutes Color at Composition of Modifier At 1 Minute At 3 Minutes to Color I 3 Minutes Clarity First Stage Final Stage Styrene/butylmethyl methacrylate (nacrylate/ethyldodecyl meracrylate; 36/4 E- E l b yellow clear captan); 36/24 (3%) butylacrylate methyl meth- (n-dodecyl acrylate/ethylmercaptan); 'acrylate 45/5 E E+ 1 k yellow opaque 50 (3%) butyl methmethyl methacrylate (tacrylate/ethyldodecyl meracrylate captan) 45/5 G+ G- 1% yellow opaque 50 (6%) butylacrylate/ methyl methbutylene diacryacrylate late; 49.5/0.5 F+ P+ 1% yellow opaque Chloride 1 P P l yellow weight. polyethylene lubricant and.0.8 parts of the glycerol monostearate internal lubricant and 0.2parts of the fatty acid ester lubricant. Composition C contains 100 parts polyvinyl chloride, 2 parts of the tin stabilizer, 0.8 parts of the glycerol monostearate internal lu-' bricant and 1.5 parts of the fatty acid ester lubricant. The unmodified'composition contains 100 parts polyvinyl chloride,2 parts of the tin stabilizer, 0.8 parts of the glycerol monostearate internal lubricant and 0.2 parts of the fatty acid ester lubricant.

EXAMPLE v11 are not suitable in the present invention (Table VIII).

EXAMPLE VIII In this example a multiphase acrylic composite polymer of the composition, first stage, 23 parts butyl acrylate/34.5 styrene/2.16 methyl methacrylate/0.24 ethyl acrylate; final stage,' 0.64 parts butyl acrylate/O.96 styrene/34.6 methylv methacrylate/3.8

clear What'is claimed is: I 1. Acompositionhaving superior roll 'release properties comprising a blend of about 75 to 99.9 weight percent vinyl halide polymer or copolymer of vinyl halide with up to about 20 percent by weight of another monovinylidene compound copolymeri-zable therewith, and about 0.1 to 25 weight percent of the multiphase acrylic composite polymer comprising to 90 weight percent-(A) a first non-crosslinked ph-ase'of viscosity.

saturated monomer; and 10 to 50 weight percent (B) a final, rigid thermoplastic phase polymerized in the presence of said first phase from an emulsion of about r 35 to 100 weight percent of at least one monomer which is methacrylate, acrylate, styrene or substituted ethyl acrylate, is prepared in'a ccordance with the procedure of Example I. The polymer is incorporated into a polyvinyl chloride composition by the procedure of Example II and is tested for roll release and mill stabilstyrene, 0 to 65 weightpercent of another acrylic monomer and 0 to 65 weight, percent of another copolymerizable ethylenically unsaturated monomer, wherein the rigid thermoplastic phase has, a viscosity average molecular weight of from about 400,000 to 5 X 10.

2. The composition of claim ide is vinyl chloride. I

3. The composition of claim 2 comprising to 99 weight percent poly (vinyl chloride-)- and l to 10 weight percent of the multiphase acrylic composite polymer.

l'wherein the vinyl hal- 

1. A COMPOSITION HAVING SUPERIOR ROLL RELEASE PROPERTIES COMPRISING OF BLEND OF ABOUT 75 TO 99.9 WEIGHT PERCENT VINYL HALIDE POLYMER OR COPOLMER OF VINYL HALIDE WITH UP TO ABOUT 20 PERCENT BY WEIGHT OF ANOTHER MONOVINYLIDENE COMPOUND COPOLYMERIZABLE THEREWITH, AND ABOUT 0.1 TO 25 WEIGHT PERCENT OF THE MULTIPHASE ACRYLIC COMPOSITE POLYMER COMPRISING 50 TO 90 WEIGHT PERCENT (A) A FIRST NON-CROSSLINKED PHASE OF VISCOSITY AVERAGE MOLECULAR WEIGHT OF ABOUT 7,500 TO 50,000 POLYMERIZED FROM A FIRST MONOMER EMULSION OF AT LEAST 25 WEIGHT PERCENT OF AT LEAST ONE ALKYL ACRYLATE WHEREIN SAID ALKYL GROUP HAS 1 TO 18 CARBON ATOMS, 0 TO 75 WEIGHT PERCENT OF ANOTHER ACRYLIC MONOMER AND 0 TO 75 PERCENT OF ANOTHER COPOLYMERIZABLE ETHYLENICALLY UNSATURATED MONOMER; AND 10 CTO 50 WEIGHT PERCENT (B) A FINAL, RIGID THERMOPLASTIC PHASE POLYMERIZED IN THE PRESENCE OF SAID FIRST PHASE FROM AN EMULSION OF ABOUT 35 TO 100 WEIGHT PERCENT OF AT LEAST ONE MONOMER WHICH IS METHACRYLATE, ACRYLATE, STYRENE OR SUBSTITUTED STYRENE, 0 TO 65 WEIGHT PERCENT OF ANOTHER COPOLYMERIZABLE ETHYLAND 0 TO 65 WEIGHT PERCENT OF ANOTHER COPOLYMERIZABLE ETHYLENICALLY UNSATURATED MONOMER, WHEREIN THE RIGID THERMOPLASTIC PHASE HAS A VISCOSITY AVERAGE MOLECULAR WEIGHT OF FROM ABOUT 400,000 TO 5 X 106
 2. The composition of claim 1 wherein the vinyl halide is vinyl chloride.
 3. The composition of claim 2 comprising 80 to 99 weight percent poly (vinyl chloride) and 1 to 10 weight percent of the multiphase acrylic composite polymer. 